In a crazy, rain-hit qualifying session, Red Bull star Vettel will start on pole for the third successive year at Montreal's Circuit Gilles Villeneuve.
However, the reigning triple world champion has so far failed to win from such a favourable position the past two years.
Vettel will have Lewis Hamilton alongside him on the front row, with the Briton starting second for the third consecutive race in his Mercedes.
At least Hamilton managed to out-pace team-mate Nico Rosberg after the German's run of three straight poles, with the 27-year-old lining up fourth.
The major surprise sees Valtteri Bottas in third, the first time this year a Williams has managed to make it into the top 10, with their highest grid slot from the first six races being 14th.
It was a qualifying session spiced up by the inclement conditions as drizzle struck just as the first session started.
Although a number of drivers chanced their arm by strapping on the supersofts to begin with, it was quickly apparent it was the wrong choice, forcing them back to the pits to switch to the intermediates more appropriate for the damp circuit.
It resulted in a hectic 20 minutes of track activity as every driver was in double digits with regard to number of laps covered.
In such circumstances Q1 produced a double surprise as Force India's Paul Di Resta and Romain Grosjean in his Lotus both failed to make into the second session.
For Di Resta, after failing to make it out of Q1 a fortnight ago in Monaco due to a team error, it is the first time in his F1 career he has suffered back-to-back exits from the opening stint and will line up 17th, as was the case two weeks ago.
Pointing an accusing finger at the Silverstone-based marque again, an angry Di Resta said: "We spent far too much time trying to fix a problem when the conditions were good when the car could have run.
"It's the fault of the team again. It's just not good enough."
Grosjean could only manage 19th, but he will start at the back of the grid - or more likely from the pit lane - given his 10-place penalty for running into the back of Daniel Ricciardo in his Toro Rosso in Monaco.
Caterham's Charles Pic starts 18th, and will have behind him Marussia duo Jules Bianchi and Max Chilton as they move up a place courtesy of Grosjean, with Giedo van der Garde in his Caterham now 21st.
A sprinkling of rain in between the opening two qualifying sessions threw another spanner into the works for those remaining.
And for Ferrari's Felipe Massa it was one to forget as he again hit a wall after twice crashing into a barrier in Monaco.
After sliding sideways to his left into the padded tyre wall, Massa slapped his hands against the steering wheel in frustration.
The shunt inevitably brought out the red flags, resulting in a seven-minute delay while marshals removed his stricken car.
With just two minutes remaining, it also led to a queue at the end of the pit lane to get back on track for one final shot at improving.
Hamilton managed to jump from ninth to top spot, whilst Force India's Adrian Sutil - who was 16th when the two-minute countdown began - clambered into the top 10.
Sauber's Nico Hulkenberg just missed out on the top 10 by 0.076secs and will start 11th, with McLaren duo Sergio Perez and Jenson Button 12th and 14th, either side of Williams' Pastor Maldonado.
It is the first time since 2003 McLaren, winners here for the last three years, have failed to get a car into the top 10.
Esteban Gutierrez will be 15th, with a disappointing Massa 16th.
Come Q1, Hamilton will feel he should be on pole as he was on course to oust Vettel from top spot, only to lock up into the penultimate corner and miss out.
Behind Rosberg will be Red Bull's Mark Webber, followed by Fernando Alonso in his Ferrari.
Another shock saw both Toro Rosso's in the top 10, with Jean-Eric Vergne seventh and Ricciardo 10th, either side of Sutil and Lotus' Kimi Raikkonen.
After clinching his 39th pole, Vettel said: "It was very tricky to adapt as you didn't know what the conditions would be, and in the end very tight with Lewis.
"Looking forward to the race, we've shown good pace and we should be good in the race, no matter the conditions.
"The forecast for tomorrow looks a little more friendly than today, we're expecting dry conditions, but there are still a lot of things that can happen on every single lap."
Hamilton, a three-time winner of this race, appreciated he had a shot at pole, only to narrowly miss out.
"I was a few tenths up, and I don't know if I would have done it or not, but I made a mistake," said Hamilton.
"I'm still happy to be starting from second."
Finnish rookie Bottas was naturally all smiles as he said: "This means a lot.
"The first six races have been so difficult, so this is a nice boost to the team. We got everything right today."
Remember to place Watch Free Live Streaming From a Different Angle on Racemate LIVE